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Na2HgTl crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Na2HgTl ribbons oriented in the (1, 0, 0) direction. Na is bonded in a linear geometry to one Hg and one Tl atom. The Na–Hg bond length is 3.18 Å. The Na–Tl bond length is 3.19 Å. Hg is bonded in a linear geometry to two equivalent Na atoms. Tl is bonded in a linear geometry to two equivalent Na atoms.
Na2HgTl crystallizes in the cubic F-43m space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded to four equivalent Tl atoms to form distorted corner-sharing NaTl4 tetrahedra. All Na–Tl bond lengths are 3.28 Å. In the second Na site, Na is bonded to four equivalent Hg atoms to form distorted corner-sharing NaHg4 tetrahedra. All Na–Hg bond lengths are 3.28 Å. Hg is bonded in a body-centered cubic geometry to four equivalent Na and four equivalent Tl atoms. All Hg–Tl bond lengths are 3.28 Å. Tl is bonded in a body-centered cubic geometry to four equivalent Na and four equivalent Hg atoms.